U.S. patent application number 10/583574 was filed with the patent office on 2007-07-05 for meso-selective synthesis of ansa-metallocenes.
This patent application is currently assigned to Basell Polyolefine GmbH. Invention is credited to Reynald Chevalier, Ludovic Delancray, Valerie Garcia, Patrik Muller, Christian Sidot, Christian Tellier.
Application Number | 20070155920 10/583574 |
Document ID | / |
Family ID | 34683639 |
Filed Date | 2007-07-05 |
United States Patent
Application |
20070155920 |
Kind Code |
A1 |
Chevalier; Reynald ; et
al. |
July 5, 2007 |
Meso-selective synthesis of ansa-metallocenes
Abstract
The present invention relates to a process for the
meso-selective preparation of ansa-metallocene complexes of the
formula (I), which comprises reacting a ligand starting compound of
the formula (II) with a transition metal compound of the formula
III, where R.sup.1, R.sup.1 are identical or different and are each
hydrogen or an organic radical having from 1 to 40 carbon atoms,
R.sup.2, R.sup.2 are identical or different and are each hydrogen
or an organic radical having from 1 to 40 carbon atoms, R.sup.3 is
a bulky organic radical which has at least 3 carbon atoms, is bound
to the oxygen atom via a nonaromatic carbon or silicon atom and may
be substituted by halogen atoms or further organic radicals having
from 1 to 20 carbon atoms and may also contain heteroatoms selected
from the group consisting of Si, N, P, O and S, T, T' are identical
or different and are each a divalent organic group which has from 1
to 40 carbon atoms and together with the cyclopentadienyl ring
forms at least one further saturated or unsaturated, substituted or
unsubstituted ring system having a ring size of from 5 to 12 atoms,
where T and T' may contain the heteroatoms Si, Ge, N, P, As, Sb, O,
S, Se or Te within the ring system fused to the cyclopentadienyl
ring, A is a bridge consisting of a divalent atom or a divalent
group, M.sup.1 is an element of group 3, 4, 5 or 6 of the Periodic
Table of the Elements or the lanthanides, the radicals X are
identical or different and are each an organic or inorganic radical
which is able to be replaced by a cyclopentadienyl anion, x is a
natural number from 1 to 4, M.sup.2 is an alkali metal, an alkaline
earth metal or a magnesium monohalide fragment, p is 1 in the case
of doubly positively charged metal ions or 2 in the case of singly
positively charged metal ions or metal ion fragments, LB is an
uncharged Lewis base ligand, and y is a natural number from 0 to 6,
and also the subsequent reaction of these complexes to form
ansa-metallocenes of the formula (IV), the use of transition metal
compounds of the formula (III) for preparing metallocenes and also
transition metal compounds of the formula (III), ansa-metallocene
complexes of the formula (I) and the use of these as constituents
of catalyst systems for the polymerization of olefines.
##STR1##
Inventors: |
Chevalier; Reynald; (Paris,
FR) ; Muller; Patrik; (Frankfurt, DE) ; Sidot;
Christian; (Compiegne, FR) ; Tellier; Christian;
(Compiegne, FR) ; Garcia; Valerie; (Compiegne,
FR) ; Delancray; Ludovic; (Cuise-la-Motte,
FR) |
Correspondence
Address: |
CONNOLLY BOVE LODGE & HUTZ, LLP
P O BOX 2207
WILMINGTON
DE
19899
US
|
Assignee: |
Basell Polyolefine GmbH
Bruhler Strasse 60
Wesseling
DE
DE 50389
|
Family ID: |
34683639 |
Appl. No.: |
10/583574 |
Filed: |
December 15, 2004 |
PCT Filed: |
December 15, 2004 |
PCT NO: |
PCT/EP04/14247 |
371 Date: |
June 19, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60542579 |
Feb 5, 2004 |
|
|
|
Current U.S.
Class: |
526/160 ; 556/16;
556/51 |
Current CPC
Class: |
C08F 110/06 20130101;
C07F 17/00 20130101; C08F 10/00 20130101; Y10S 526/943 20130101;
C08F 10/00 20130101; C08F 4/65927 20130101 |
Class at
Publication: |
526/160 ;
556/051; 556/016 |
International
Class: |
C07F 17/00 20060101
C07F017/00; C08F 4/44 20060101 C08F004/44 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 19, 2003 |
DE |
103 60 060.4 |
Claims
1-10. (canceled)
11. A process for meso-selective preparation of ansa-metallocene
complexes of formula (I): ##STR11## which comprises reacting a
ligand starting compound of formula (II): ##STR12## with a
transition metal compound of formula (III):
(LB).sub.yM.sup.1(OR.sup.3)X.sub.x+1 (III) where R.sup.1, R' are
identical or different and are each hydrogen or an organic radical
having from 1 to 40 carbon atoms; R.sup.2, R.sup.2' are identical
or different and are each hydrogen or an organic radical having
from 1 to 40 carbon atoms; R.sup.3 is a bulky organic radical
comprising at least 3 carbon atoms, and is bound to the oxygen atom
via a nonaromatic carbon or silicon atom, and may be substituted by
halogen atoms or further organic radicals comprising from 1 to 20
carbon atoms, and optionally comprise at least one heteroatom
selected from the group consisting of Si, N, P, O and S; T, T' are
identical or different and are each a divalent organic group
comprising from 1 to 40 carbon atoms, and together with the
cyclopentadienyl rings form at least one further saturated or
unsaturated, substituted or unsubstituted ring system comprising
from 5 to 12 atoms, where T and T' optionally comprises at least
one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
M.sup.1 is at least one lanthanide or an element of group 3, 4, 5
or 6 of the Periodic Table of Elements; X are identical or
different and are each an organic or inorganic radical which is
able to be replaced by a cyclopentadienyl anion; x is a natural
number from 1 to 4; M.sup.2 is an alkali metal, an alkaline earth
metal, or a magnesium monohalide fragment; p is 1 when M.sup.2 is a
doubly positively charged metal ion, or 2 when M.sup.2 is a singly
positively charged metal ion or metal ion fragment; LB is an
uncharged Lewis base ligand; and y is a natural number from 0 to
6.
12. The process as claimed in claim 11, wherein the
ansa-metallocene complexes of formula (I) is converted into an
ansa-metallocene complex of formula (IV): ##STR13## where R.sup.1,
R.sup.1' are identical or different and are each hydrogen or an
organic radical having from 1 to 40 carbon atoms; R.sup.2, R.sup.2'
are identical or different and are each hydrogen or an organic
radical having from 1 to 40 carbon atoms; T, T' are identical or
different and are each a divalent organic group comprising from 1
to 40 carbon atoms, and together with the cyclopentadienyl rings
form at least one further saturated or unsaturated, substituted or
unsubstituted ring system comprising from 5 to 12 atoms, where T
and T' optionally comprises at least one heteroatom selected from
Si, Ge, N, P, As, Sb, O, S, Se or Te; A is a bridge consisting of a
divalent atom or a divalent group; M.sup.1 is at least one
lanthanide or an element of group 3, 4, 5 or 6 of the Periodic
Table of Elements; X are identical or different and are each an
organic or inorganic radical which is able to be replaced by a
cyclopentadienyl anion; and x is a natural number from 1 to 4;
comprising reacting the ansa-metallocene complexes of formula (I)
with at least one suitable elimination reagent in a subsequent
reaction step.
13. The process as claimed in claim 11, wherein R.sup.1, R' are
identical or different and are each a C.sub.1-C.sub.10-alkyl;
R.sup.2, R.sup.2' are each hydrogen; T, T' are identical or
different and are each an unsubstituted 1,3-butadiene-1,4-diyl
group or a 1,3-butadiene-1,4-diyl group substituted with from 1 to
4 R.sup.4 radicals, where R.sup.4 can be identical or different and
are organic radicals having from 1 to 40 carbon atoms; and A is
ethylene, substituted ethylene or substituted silylene.
14. The process as claimed in claim 12, wherein R.sup.1, R.sup.1'
are identical or different and are each a C.sub.1-C.sub.10-alkyl;
R.sup.2, R.sup.2' are each hydrogen; T, T' are identical or
different and are each an unsubstituted 1,3-butadiene-1,4-diyl
group or a 1,3-butadiene-1,4-diyl group substituted with from 1 to
4 R.sup.4 radicals, where R.sup.4 can be identical or different and
are organic radicals having from 1 to 40 carbon atoms; and A is
ethylene, substituted ethylene or substituted silylene.
15. The process as claimed in claim 11, wherein R.sup.3 is an alkyl
radical branched in an a position, and comprises from 4 to 40
carbon atoms, and is optionally substituted by at least one halogen
atom or organic radical comprising from 1 to 10 carbon atoms;
M.sup.1 is Ti, Zr or Hf; X is halogen; x is 2; LB is a cyclic or
acyclic ether or diether; and y is 1 or 2.
16. The process as claimed in claim 12, wherein R.sup.3 is an alkyl
radical branched in an .alpha. position, and comprises from 4 to 40
carbon atoms, and is optionally substituted by at least one halogen
atom or organic radical comprising from 1 to 10 carbon atoms;
M.sup.1 is Ti, Zr or Hf; X is halogen; x is 2; LB is a cyclic or
acyclic ether or diether; and y is 1 or 2.
17. The process as claimed in claim 11, wherein M.sup.2 is Li, Na,
K, MgCl, MgBr, Mgl or Mg.
18. The process as claimed in claim 12, wherein M.sup.2 is Li, Na,
K, MgCl, MgBr, Mgl or Mg.
19. A method for preparing ansa-metallocene complexes comprising
reacting a metallocene complex with a transition metal compound of
formula (III): (LB).sub.yM.sup.1(OR.sup.3)X.sub.x+1 (III)
20. A transition metal compound of the formula (III):
(LB).sub.yM.sup.1(OR.sup.3).sub.x+1 (III) where R.sup.3 is a bulky
organic radical comprising at least 3 carbon atoms, and is bound to
the oxygen atom via a nonaromatic carbon or silicon atom, and may
be substituted by halogen atoms or further organic radicals
comprising from 1 to 20 carbon atoms, and optionally comprise at
least one heteroatom selected from the group consisting of Si, N,
P, O and S; M.sup.1 is at least one lanthanide or an element of
group 3, 4, 5 or 6 of the Periodic Table of Elements; X are
identical or different and are each an organic or inorganic radical
which is able to be replaced by a cyclopentadienyl anion; x is a
natural number from 1 to 4; LB is an uncharged Lewis base ligand;
and y is a natural number from 0 to 6.
21. A method for preparing ansa-metallocene complexes of formula
(IV) comprising reacting a metallocene complex of formula (I):
##STR14## where R.sup.1, R.sup.1' are identical or different and
are each hydrogen or an organic radical having from 1 to 40 carbon
atoms; R.sup.2, R.sup.2' are identical or different and are each
hydrogen or an organic radical having from 1 to 40 carbon atoms;
R.sup.3 is a bulky organic radical comprising at least 3 carbon
atoms, and is bound to the oxygen atom via a nonaromatic carbon or
silicon atom, and may be substituted by halogen atoms or further
organic radicals comprising from 1 to 20 carbon atoms, and
optionally comprise at least one heteroatom selected from the group
consisting of Si, N, P, O and S; T, T' are identical or different
and are each a divalent organic group comprising from 1 to 40
carbon atoms, and together with the cyclopentadienyl rings form at
least one further saturated or unsaturated, substituted or
unsubstituted ring system comprising from 5 to 12 atoms, where T
and T' optionally comprises at least one heteroatom selected from
Si, Ge, N, P, As, Sb, O, S, Se or Te; A is a bridge consisting of a
divalent atom or a divalent group; M.sup.1 is at least one
lanthanide or an element of group 3, 4, 5 or 6 of the Periodic
Table of Elements; X are identical or different and are each an
organic or inorganic radical which is able to be replaced by a
cyclopentadienyl anion; and x is a natural number from 1 to 4; with
a transition metal compound.
22. An ansa-metallocene complex of formula (I): ##STR15## where
R.sup.1, R.sup.1' are identical or different and are each hydrogen
or an organic radical having from 1 to 40 carbon atoms; R.sup.2,
R.sup.2' are identical or different and are each hydrogen or an
organic radical having from 1 to 40 carbon atoms; T, T' are
identical or different and are each a divalent organic group
comprising from 1 to 40 carbon atoms, and together with the
cyclopentadienyl rings form at least one further saturated or
unsaturated, substituted or unsubstituted ring system comprising
from 5 to 12 atoms, where T and T' optionally comprises at least
one heteroatom selected from Si, Ge, N, P, As, Sb, O, S, Se or Te;
A is a bridge consisting of a divalent atom or a divalent group;
R.sup.3 is an alkyl radical branched in an a position, and
comprises from 4 to 40 carbon atoms, and is optionally substituted
by at least one halogen atom or organic radical comprising from 1
to 10 carbon atoms; M.sup.1 is Ti, Zr or Hf; x is halogen; and x is
2.
23. A constituent of a catalyst system for polymerizing at least
one olefin comprising an ansa-metallocene complex of formula (I):
##STR16## R.sup.1, R.sup.1' are identical or different and are each
hydrogen or an organic radical having from 1 to 40 carbon atoms;
R.sup.2, R.sup.2' are identical or different and are each hydrogen
or an organic radical having from 1 to 40 carbon atoms; R.sup.3 is
a bulky organic radical comprising at least 3 carbon atoms, and is
bound to the oxygen atom via a nonaromatic carbon or silicon atom,
and may be substituted by halogen atoms or further organic radicals
comprising from 1 to 20 carbon atoms, and optionally comprise at
least one heteroatom selected from the group consisting of Si, N,
P, O and S; T, T' are identical or different and are each a
divalent organic group comprising from 1 to 40 carbon atoms, and
together with the cyclopentadienyl rings form at least one further
saturated or unsaturated, substituted or unsubstituted ring system
comprising from 5 to 12 atoms, where T and T' optionally comprises
at least one heteroatom selected from Si, Ge, N, P, As, Sb, O, S,
Se or Te; A is a bridge consisting of a divalent atom or a divalent
group; M.sup.1 is at least one lanthanide or an element of group 3,
4, 5 or 6 of the Periodic Table of Elements; X are identical or
different and are each an organic or inorganic radical which is
able to be replaced by a cyclopentadienyl anion; and x is a natural
number from 1 to 4.
Description
[0001] The present invention relates to a process for the
meso-selective preparation of ansa-metallocene complexes of the
formula (I), the subsequent reaction of these complexes to form
ansa-metallocenes of the formula (I), the use of transition metal
compounds of the formula (III) for preparing metallocenes and also
transition metal compounds of the formula (III), ansa-metallocene
complexes of the formula (I) and the use of these as constituents
of catalyst systems for the polymerization of olefins.
[0002] Research and development on the use of organic transition
metal compounds, in particular metallocenes, as catalyst components
for the polymerization and copolymerization of olefins with the
objective of preparing tailored polyolefins has been pursued
vigorously in universities and in industry over the past 15
years.
[0003] Now, not only the ethylene-based polyolefins prepared by
means of metallocene catalyst systems and also, in particular, the
propylene-based polyolefins prepared by means of metallocene
catalyst systems represent a dynamically growing market
segment.
[0004] To prepare isotactic polypropylenes, ansa-metallocenes in
their racemic form are generally used. In the synthesis of the
racemic ansa-metallocenes, these are generally obtained together
with the undesired meso-metallocenes which are usually separated
off without the meso-metallocenes being able to be isolated. It is
generally known that ansa-metallocenes in the meso form are
responsible for the formation of atactic polypropylenes when used
as catalyst constituents.
[0005] EP 0 643 078 describes the use of a particular
ansa-metallocene in the meso form for preparing very high molecular
weight homopolymers and copolymers of ethylene.
[0006] While in the case of racemic metallocenes, various
racemoselective syntheses have been developed, there has hitherto
not yet been an urgent need to develop corresponding meso-selective
syntheses.
[0007] Organometallics 1997, 16, 5046-49, describes the synthesis
of a meso-metallocene or of the corresponding rac-metallocene, in
which precisely one of the two possible metallocene forms was
formed starting from an isolated diastereomer of a distannylated
biscyclopentadienyl ligand system. However, the diastereomerically
pure distannylated biscyclopentadienyl ligand system had previously
been obtained by separation of the corresponding mixture of
diastereomers.
[0008] The literature also describes cases in which the rac/meso
ratios of the metallocene isomers were dependent on the solvent
used in the syntheses starting from zirconium tetrachloride and
various dilithiated biscyclopentadienyl ligand systems, but no
standard rules were able to be derived.
[0009] The known methods of preparing particular ansa-metallocenes
in the meso form leave something to be desired both in respect of
the economics and in respect of the applicability.
[0010] To be able to obtain a better assessment of the potential of
ansa-metallocenes in the meso form, there is a need for various
meso-metallocenes to be able to be obtained in a simple
fashion.
[0011] It is an object of the present invention to discover a
simple, economical and widely applicable process for preparing
ansa-metallocenes in the meso form, which offers advantages both in
terms of economics and in terms of the applicability.
[0012] We have found that this object is achieved by a process for
the meso-selective preparation of ansa-metallocene complexes of the
formula (I), ##STR2## which comprises reacting a ligand starting
compound of the formula (II) ##STR3## with a transition metal
compound of the formula (III) (LB).sub.yM.sup.1(OR.sup.3)X.sub.x+1
(III) where [0013] R.sup.1, R.sup.1' are identical or different and
are each hydrogen or an organic radical having from 1 to 40 carbon
atoms, [0014] R.sup.2, R.sup.2' are identical or different and are
each hydrogen or an organic radical having from 1 to 40 carbon
atoms, [0015] R.sup.3 is a bulky organic radical which has at least
3 carbon atoms, is bound to the oxygen atom via a nonaromatic
carbon or silicon atom and may be substituted by halogen atoms or
further organic radicals having from 1 to 20 carbon atoms and may
also contain heteroatoms selected from the group consisting of Si,
N, P, O and S, [0016] T, T' are identical or different and are each
a divalent organic group which has from 1 to 40 carbon atoms and
together with the cyclopentadienyl ring forms at least one further
saturated or unsaturated, substituted or unsubstituted ring system
having a ring size of from 5 to 12 atoms, where T and T' may
contain the heteroatoms Si, Ge, N, P, As, Sb, O, S, Se or Te within
the ring system fused to the cyclopentadienyl ring, [0017] A is a
bridge consisting of a divalent atom or a divalent group, [0018] M'
is an element of group 3, 4, 5 or 6 of the Periodic Table of the
Elements or the lanthanides, [0019] the radicals x are identical or
different and are each an organic or inorganic radical which is
able to be replaced by a cyclopentadienyl anion, [0020] x is a
natural number from 1 to 4, [0021] M.sup.2 is an alkali metal, an
alkaline earth metal or a magnesium monohalide fragment, [0022] p
is 1 in the case of doubly positively charged metal ions or 2 in
the case of singly positively charged metal ions or metal ion
fragments, [0023] LB is an uncharged Lewis base ligand, [0024] and
[0025] y is a natural number from 0 to 6. The radicals R.sup.1 and
R.sup.1' are identical or different, preferably identical, and are
each hydrogen or an organic radical having from 1 to 40 carbon
atoms, for example C.sub.1-C.sub.40-alkyl,
C.sub.1-C.sub.10-fluoroalkyl, C.sub.2-C.sub.40-alkenyl,
C.sub.6-C.sub.40-aryl, C.sub.6-C.sub.10-fluoroaryl, arylalkyl,
arylalkenyl or alkylaryl each having from 1 to 10, preferably from
1 to 4, carbon atoms in the alkyl part and from 6 to 22, preferably
from 6 to 10, carbon atoms in the aryl part, or a
C.sub.2-C.sub.40-heteroaromatic radical which contains at least one
heteroatom selected from the group consisting of the elements O, N,
S, P and Se, in particular O, N and S, and may be substituted by
further radicals R.sup.6, where R.sup.6 is an organic radical
having from 1 to 20 carbon atoms, for example C.sub.1-C.sub.10-,
preferably C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.15-, preferably
C.sub.6-C.sub.10-aryl, alkylaryl, arylalkyl, fluoroalkyl or
fluoroaryl each having from 1 to 10, preferably from 1 to 4, carbon
atoms in the alkyl radical and from 6 to 18, preferably from 6 to
10, carbon atoms in the aryl radical, and a plurality of radicals
R.sup.6 can be identical or different.
[0026] Preference is given to R.sup.1 and R.sup.1' being identical
or different, preferably identical, and each being
C.sub.1-C.sub.10-alkyl such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl,
cyclohexyl, n-heptyl or n-octyl, preferably methyl, ethyl or
isopropyl, in particular methyl.
[0027] The radicals R.sup.2 and R.sup.2' are identical or
different, preferably identical, and are each hydrogen or an
organic radical having from 1 to 40 carbon atoms, for example
C.sub.1-C.sub.40-alkyl, C.sub.1-C.sub.10-fluoroalkyl,
C.sub.2-C.sub.40-alkenyl, C.sub.6-C.sub.40-aryl,
C.sub.6-C.sub.10-fluoroaryl, arylalkyl, arylalkenyl or alkylaryl
each having from 1 to 10, preferably from 1 to 4, carbon atoms in
the alkyl part and from 6 to 22, preferably from 6 to 10, carbon
atoms in the aryl part, or a C.sub.2-C.sub.40-heteroaromatic
radical which contains at least one heteroatom selected from the
group consisting of the elements O, N, S, P and Se, in particular
O, N and S, and may be substituted by further radicals R.sup.6, as
defined above, and a plurality of radicals R.sup.6 can be identical
or different. Preference is given to R.sup.2 and R.sup.2' each
being hydrogen.
[0028] The radical R.sup.3 is a bulky organic radical which has at
least 3 carbon atoms, preferably from 4 to 40 carbon atoms, is
bound to the oxygen atom via a nonaromatic carbon or silicon atom,
preferably a carbon atom, and may be substituted by halogen atoms
or further organic radicals having from 1 to 20 carbon atoms and
may also contain heteroatoms selected from the group consisting of
Si, N, P, O and S, preferably N, O and S. A nonaromatic carbon or
silicon atom is an atom of this type which is not located within an
aromatic or heteroaromatic ring system, i.e. the oxygen atom of the
OR.sup.3 group is not bound directly to an aromatic or
heteroaromatic radical. Examples of such bulky alkyl radicals are
isopropyl, cyclohexyl, tert-butyl, 1-adamantyl, 2-adamantyl,
triphenylmethyl, diphenylmethyl,
(1R)-endo-(+)-1,3,3-trimethyl-2-norbornyl, trimethylsilyl,
triphenylsilyl and dimethyl-tert-butylsilyl.
[0029] R.sup.3 is preferably an alkali radical which is branched in
the .alpha. position and has from 4 to 40, preferably from 7 to 40,
carbon atoms and may be substituted by halogen atoms such as
fluorine, chlorine, bromine or iodine, in particular fluorine or
chlorine, or organic radicals having from 1 to 10 carbon atoms. In
this context, an alkyl radical which is branched in the .alpha.
position is an alkyl radical whose linking .alpha. atom bears at
least two directly bound atoms which are different from hydrogen
and not more than one directly bound hydrogen atom.
[0030] R.sup.3 is particularly preferably a bicyclic or polycyclic
alkyl radical which has from 7 to 30 carbon atoms and may be
substituted by one or more C.sub.1-C.sub.4-alkyl radicals.
[0031] T and T' are identical or different, preferably identical,
and are each a divalent organic group which has from 1 to 40 carbon
atoms and together with the cyclopentadienyl ring forms at least
one further saturated or unsaturated, substituted or unsubstituted
ring system having a ring size of from 5 to 12, in particular from
5 to 7, atoms, where T and T' may contain the heteroatoms Si, Ge,
N, P, As, Sb, O, S, Se or Te, preferably Si, N, O or S, in
particular S or N, within the ring system fused to the
cyclopentadienyl ring.
[0032] Examples of preferred divalent organic groups T or T' are
##STR4## preferably ##STR5## in particular ##STR6## where the
radicals R.sup.4 are identical or different and are each an organic
radical having from 1 to 40, preferably from 1 to 20, carbon atoms,
for example cyclic, branched or unbranched C.sub.1-C.sub.20-,
preferably C.sub.1-C.sub.8-alkyl radicals, C.sub.2-C.sub.20-,
preferably C.sub.2-C.sub.8-alkenyl radicals, C.sub.6-C.sub.22-,
preferably C.sub.6-C.sub.10-aryl radicals, alkylaryl or arylalkyl
radicals each having from 1 to 10, preferablyfrom 1 to 4, carbon
atoms in the alkyl part and from 6 to 22, preferably from 6 to 10,
carbon atoms in the aryl part, where the radicals may also be
halogenated, or the radicals R.sup.4 are substituted or
unsubstituted, saturated or unsaturated, in particular aromatic,
heterocyclic radicals which have from 2 to 40, in particular from 4
to 20, carbon atoms and contain at least one heteroatom which is
preferably selected from the group consisting of the elements O, N,
S and P, in particular O, N and S, or two adjacent radicals R.sup.4
together with the atoms connecting them form a monocyclic or
polycyclic, substituted or unsubstituted ring system which has from
1 to 40 carbon atoms and may also contain heteroatoms selected from
the group consisting of the elements Si, Ge, N, P, O, S, Se and Te,
in particular N or S, [0033] R.sup.5 is hydrogen or is as defined
for R.sup.4, [0034] s is a natural number from 0 to 4, in
particular from 0 to 3, [0035] t is a naturalenumber from 0 to 2,
in particular 1 or 2, and [0036] u is a natural number from 0 to 6,
in particular 1.
[0037] A is a bridge consisting of a divalent atom or a divalent
group. Examples of A are: ##STR7## [0038] --B(R.sup.7)--,
--B(NR.sup.7R.sup.8)--, --Al(R.sup.7)--, --O--, --S--, --S(O)--,
--S((O).sub.2)--, --N(R.sup.7)--, --C(O)--, --P(R.sup.7)-- or
--P(O) (R .sup.7)--, in particular ##STR8## where [0039] M.sup.3 is
silicon, germanium or tin, preferably silicon or germanium,
particularly preferably silicon, and [0040] R.sup.7, R.sup.8 and
R.sup.9 are identical or different and are each a hydrogen atom, a
halogen atom, a trimethylsilyl group, a C.sub.1-C.sub.10-,
preferably C.sub.1-C.sub.3-alkyl group, a
C.sub.1-C.sub.10-fluoroalkyl group, a C.sub.6-C.sub.10-fluoroaryl
group, a C.sub.6-C.sub.10-aryl group, a C.sub.1-C.sub.1-,
preferably C.sub.1-C.sub.3-alkoxy group, a
C.sub.7-C.sub.15-alkylaryloxy group, a C.sub.2-C.sub.10-,
preferably C.sub.2-C.sub.4-alkenyl group, a
C.sub.7-C.sub.40-arylalkyl group, a C.sub.8-C.sub.40arylalkenyl
group or a C.sub.7-C.sub.40-alkylaryl group or two adjacent
radicals together with the atoms connecting them form a saturated
or unsaturated ring having from 4to 15 carbon atoms.
[0041] Preferred embodiments of A are the bridges:
dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl,
dimethylgermandiyl, ethylidene, 1-methylethylidene,
1,1-dimethylethylidene, 1,2-dimethylethylidene,
1,1,2,2-tetramethylethylidene, dimethylmethylidene,
phenylmethylmethylidene or diphenylmethylidene, in particular
dimethylsilanediyl, diphenylsilanediyl and ethylidene.
[0042] A is particularly preferably a substituted silylene group or
a substituted or unsubstituted ethylene group, preferably a
substituted silylene group such as dimethylsilanediyl,
methylphenylsilanediyl, methyl-tert-butylsilanediyl or
diphenylsilanediyl, in particular dimethylsilanediyl.
[0043] M.sup.1 is an element of group 3, 4, 5 or 6 of the Periodic
Table of the Elements or the lanthanides, for example titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chromium,
molybdenum or tungsten, preferably titanium, zirconium or hafnium,
particularly preferably zirconium or hafnium and very particularly
preferably zirconium.
[0044] The radicals X are identical or different and are each an
organic or inorganic radical which is able to be replaced by a
cyclopentadienyl anion. Examples of X are halogen such as chlorine,
bromine, iodine, in particular chlorine, organosulfonate groups
such as trifluoromethanesulfonate (triflate) or mesylate. X is
preferably halogen, in particular chlorine.
[0045] x is a natural number from 1 to 4 and usually corresponds to
the oxidation number of M.sup.1 minus 2. In the case of elements of
group 4 of the Periodic Table of the Elements, x is preferably
2.
[0046] M.sup.2 is an alkali metal such as Li, Na or K, an alkaline
earth metal such as Mg or Ca, in particular Mg, or a magnesium
monohalide fragment such as MgCl, MgBr or Mgl. M.sup.2 is
preferably Li, Na, K, MgCl, MgBr, Mgl or Mg, particularly
preferably Li, K or Mg, in particular Li.
[0047] p is 1 for doubly positively charged metal ions or 2 for
singly positively charged metal ions or metal ion fragments.
[0048] LB is an uncharged Lewis base ligand, preferably a linear,
cyclic or branched oxygen-, sulfur, nitrogen- or
phosphorus-containing, in particular oxygen- or
nitrogen-containing, hydrocarbon such as an ether, polyether,
thioether, amine, polyamine or phosphine. LB is preferably a cyclic
or acyclic ether or diether, for example diethyl ether, dibutyl
ether, tert-butyl methyl ether, anisole, dimethoxyethane (DME),
tetrahydrofuran (THF) or dioxane. Particular preference is given to
THF or DME.
[0049] y is a natural number from 0 to 6. In the case of elements
of group 4 of the Periodic Table of the Elements, y is preferably 1
or 2.
[0050] Furthermore, the substituents according to the present
invention are, unless restricted further, defined as follows:
[0051] The term "organic radical having from 1 to 40 carbon atoms"
as used in the present context refers, for example, to
C.sub.1-C.sub.40-alkyl radicals, C.sub.1-C.sub.10-fluoroalkyl
radicals, C.sub.1-C.sub.12-alkoxy radicals, saturated
C.sub.3-C.sub.20-heterecyclic radicals, C.sub.6-C.sub.40-aryl
radicals, C.sub.2-C40-heteroaromatic radicals,
C.sub.6-C.sub.10-fluoroaryl radicals, C.sub.6-C.sub.10-aryloxy
radicals, C.sub.3-C.sub.18-trialkylsilyl radicals,
C.sub.2-C.sub.20-alkenyl radicals, C.sub.2-C.sub.20-alkynyl
radicals, C.sub.7-C.sub.40-arylalkyl radicals or
C.sub.8-C.sub.40-arylalkenyl radicals. An organic radical is in
each case derived from an organic compound. Thus, the organic
compound methanol can in principle give rise to three different
organic radicals having one carbon atom, namely methyl
(H.sub.3C--), methoxy (H.sub.3C--O--) and hydroxymethyl
(HOC(H.sub.2)--).
[0052] The term "alkyl" as used in the present context encompasses
linear or singly or multiply branched saturated hydrocarbons which
may also be cyclic. Preference is given to a C.sub.1-C.sub.18-alkyl
group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl,
isopropyl, isobutyl, isopentyl, isohexyl, sec-butyl or
tert-butyl.
[0053] The term "alkenyl" as used in the present context
encompasses linear or singly or multiply branched hydrocarbons
having at least one, if desired more than one, C-C double bonds
which may be cumulated or alternating.
[0054] The term "saturated heterocyclic radical" as used in the
present context refers, for example, to monocyclic or polycyclic,
substituted or unsubstituted hydrocarbon radicals in which one or
more carbon atoms, CH groups and/or CH.sub.2 groups have been
replaced by heteroatoms which are preferably selected from the
group consisting of O, S, N and P. Preferred examples of
substituted or unsubstituted saturated heterocyclic radicals are
pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl,
piperazinyl, morpholinyl, tetrahydrofuranyl, tetrahydropyranyl,
tetrahydrothienyl and the like, and also methyl-, ethyl-, propyl-,
isopropyl- and tert-butyl-substituted derivatives thereof.
[0055] The term "aryl" as used in the present context refers, for
example, to aromatic and fused or unfused polyaromatic hydrocarborn
substituents which may be monosubstituted or polysubstituted by
linear or branched C.sub.1-C.sub.18-alkyl, C.sub.1-C.sub.18-alkoxy,
C.sub.2-C.sub.10-alkenyl or halogen, in particular fluorine.
Preferred examples of substituted and unsubstituted aryl radicals
are, in particular, phenyl, pentafluorophenyl, 4-methylphenyl,
4-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl,
4-tert-butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthryl,
9-phenanthryl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl and
4-trifluoromethylphenyl.
[0056] The term "heteroaromatic radical" as used in the present
context refers, for example, to aromatic hydrocarbon radicals in
which one or more carbon atoms have been replaced by nitrogen,
phosphorus, oxygen or sulfur atoms or combinations thereof. They
may, like the aryl radicals, be monosubstituted or polysubstituted
bylinear or branched C.sub.1-C.sub.18-alkyl,
C.sub.2-C.sub.10-alkenyl or halogen, in particular fluorine.
Preferred examples are furyl, thienyl, pyrrolyl, pyridyl,
pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyrimidinyl, pyrazinyl
and the like, and also methyl-, ethyl-, propyl-, isopropyl- and
tert-butyl-substituted derivatives thereof.
[0057] The term "arylalkyl" as used in the present context refers,
for example, to aryl-containing substituents whose aryl radical is
connected via an alkyl chain to the remainder of the molecule.
Preferred examples are benzyl, substitutued benzyl, phenethyl,
substituted phenethyl and the like.
[0058] The terms fluoroalkyl and fluoroaryl indicate that at least
one hydrogen atom, preferably two or more and at most all hydrogen
atoms, of the respective substituent have been replaced by fluorine
atoms. Examples of fluorine-containing substituents which are
preferred according to the present invention are trifluoromethyl,
2,2,2-trifluoroethyl, pentafluorophenyl, 4-trifluoromethylphenyl,
4-perfluoro-tert-butylphenyl and the like.
[0059] In a preferred embodiment of the process of the present
invention, the metallocene complex of the formula (I) is converted
into an ansa-metallocene complex of the formula (IV) ##STR9## where
the variables and indices have the same meanings as in the formula
(I), by reaction with suitable elimination reagents in a subsequent
reaction step.
[0060] The present invention therefore also provides for the use of
a metallocene complex of the formula (I) as intermediate for
preparing ansa-metallocene complexes of the formula (IV).
[0061] Elimination reagents are known in principle. Examples of
preferred elimination reagents are hydrogen halides, for example
HCl, and aliphatic or aromatic carboxylic halides, for example
acetyl chloride, acetyl bromide, phenylacetyl chloride,
tert-butylacetyl chloride, and also organoaluminum halides, for
example ethylaluminum dichloride, methylaluminum dichloride or
dimethylaluminum chloride, and halogen-containing main group
compounds such as SiCl.sub.4, SOCl.sub.2, PCl.sub.5 or
AlCl.sub.3.
[0062] Particularly preferred elimination reagents are HCl, acetyl
chloride, ethylaluminum dichloride and methylaluminum
dichloride.
[0063] The elimination reaction is usually carried out in a
temperature range from 0.degree. C. to 110.degree. C. To complete
the reaction, it is usual to use at least stoichiometric amounts of
the elimination reagent.
[0064] Excess elimination reagent generally does not interfere as
long as it can be separated off from the target product without
problems in the work-up.
[0065] Particular preference is given to a process for the
meso-selective preparation of ansa-metallocene complexes of the
formula (I) which optionally further comprises the subsequent
reaction of these complexes to form ansa-metallocenes of the
formula (IV)
in which
[0066] R.sup.1, R.sup.1.sup.1 are identical or different and are
each C.sub.1-C.sub.10-alkyl such as methyl, ethyl, isopropyl,
tert-butyl, cyclohexyl or octyl, in particular methyl, [0067]
R.sup.2, R.sup.2' are each hydrogen, [0068] T, T' are identical or
different and are each an unsubstituted 1,3-butadiene-1,4-diyl
group or a 1,3-butadiene-1,4-diyl group substituted by from 1 to 4
radicals R.sup.4, where R.sup.4 can be identical or different and
are organic radicals having from 1 to 40 carbon atoms, [0069] A is
ethylene, substituted ethylene or substituted silylene, in
particular substituted silylene such as dimethylsilanediyl,
methylphenylsilanediyl, methyl-tert-butylsilanediyl or
diphenylsilanediyl, in particular dimethylsilanediyl, and the
variables R.sup.3, M.sup.1, X, M.sup.2 and LB and also the indices
x, p and y are as defined for the formula I.
[0070] Very particular preference is given to a process for the
meso-selective preparation of ansa-metallocene complexes of the
formula (I) or the formula (IV), as described above,
in which
[0071] R.sup.3 is an alkyl radical which is branched in the .alpha.
position and has from 4 to 40, preferably from 7 to 40, carbon
atoms and may be substituted by halogen atoms such as fluorine,
chlorine, bromine or iodine, in particular fluorine or chlorine, or
by organic radicals having from 1 to 10 carbon atoms, with R.sup.3
particularly preferably being a bicyclic or polycyclic alkyl
radical which has from 7 to 30 carbon atoms and may be substituted
by one or more C.sub.1-C.sub.4-alkyl radicals, [0072] M.sup.1 is
Ti, Zr or Hf, preferably Zr or Hf, in particular Zr, [0073] X is
halogen, in particular chlorine, [0074] x is 2, [0075] LB is
acyclic or acyclic ether or diether, in particular THF or DME, and
[0076] y is 1 or 2.
[0077] In the process of the present invention, the salt-like
ligand starting compounds of the formula (II) can either be used in
isolated form or be prepared in-situ immediately before the
reaction with the transition metal compound of the formula
(III).
[0078] To synthesize the salt-like ligand starting compounds of the
formula (II), the corresponding uncharged bridged
biscyclopentadienyl compound is usually doubly deprotonated by
means of a strong base. Strong bases which can be used are, for
example, organometallic compounds or metal hydrides, preferably
compounds containing an alkali metal or an alkaline earth metal.
Preferred bases are organolithium or organomagnesium compounds such
as methyllithium, n-butyllithium, sec-butyllithium,
n-butyl-n-octylmagnesium or dibutylmagnesium.
[0079] The uncharged bridged biscyclopentadienyl compound to be
deprotonated can also be used in isolated form or without
isolation, prepared directly by the coupling reaction of two
cyclopentadienyl anions with an appropriate bridging reagent, for
example a diorganodichlorosilane such as dimethyldichlorosilane. A
further possible way of preparing the uncharged biscyclopentadienyl
compounds is stepwise construction. Here, for example, a
cyclopentadienyl anion is firstly reacted with an appropriate
bridging reagent, for example a diorganodichlorosilane such as
dimethyldichlorosilane, to form a
monochloromonocyclopentadienyldiorganosilane compound and the
chlorine in this is subsequently replaced by a further
cyclopentadienyl radical, which may be different from the first
cyclopentadienyl radical, to obtain the desired uncharged bridged
biscyclopentadienyl compound.
[0080] The synthesis of the cyclopentadienyl anions can in
principle be carried out under the same conditions as the
deprotonation of the uncharged bridged biscyclopentadienyl
compound.
[0081] The double deprotonation of the uncharged bridged
biscyclopentadienyl compound to form the ligand starting compound
of the formula (II) is usually carried out at from -78.degree. C.
to 11 0.degree. C., preferably from 0.degree. C. to 80.degree. C.
and particularly preferably from 20.degree. C. to 70.degree. C.
[0082] Suitable inert solvents in which the deprotonation of the
cyclopentadienyl derivatives by means of strong bases can be
carried out are aliphatic or aromatic hydrocarbons such as benzene,
toluene, xylene, mesitylene, ethylbenzene, cumene, decalin,
tetralin, pentane, hexane, cyclohexane, heptane or ethers such as
diethyl ether, di-n-butyl ether, tert-butyl methyl ether (MTBE),
tetrahydrof uran (THF), 1,2-dimethoxyethane (DME), anisole,
triglyme, dioxane and any mixtures of these substances. Preference
is given to solvents or solvent mixtures in which the subsequent
process of the present invention for preparing the metallocene
complexes of the formula (I) can likewise be carried out
directly.
[0083] The synthesis of the transition metal compounds of the
formula (III) is in principle known from the literature. A possible
way of preparing them is, for example, reaction of a transition
metal compound M.sup.1X.sub.x+2 or (LB).sub.YM.sup.1X.sub.x+2 with
a metal alkoxide M.sup.2(OR.sup.3) in an inert solvent, where
M.sup.2' and M.sup.2 and the other variables are as defined for the
formula (I).
[0084] In the process of the present invention, the reaction of the
ligand starting compound of the formula (II) with the transition
metal compound of the formula (III) can be carried out in an inert
solvent or solvent mixture at from -78.degree. C. to 150.degree.
C., in particular from 0.degree. C. to 110.degree. C. The inert
solvents or solvent mixtures which can be used are preferably the
same ones in which the-synthesis of the ligand starting compound of
the formula (II) has been carried out. The reaction times are
usually at least 10 minutes, generally from 1 to 8 hours.
[0085] The present invention therefore also provides for the use of
a transition metal compound of the formula (III)
(LB).sub.yM.sup.1(OR.sup.3)X.sub.x+1 (III) for the preparation of
ansa-metallocene complexes, in particular for the meso-selective
preparation of ansa-metallocene complexes of the formula (I) or for
the preparation of ansa-metallocene complexes of the formula (IV)
by the process of the present invention, where the variables and
indices are as described above.
[0086] The present invention further provides transition metal
compounds of the formula (III) (LB).sub.yM.sup.1(OR.sup.3)X.sub.x+1
(III) where the variables and indices are as described above.
[0087] Particular preference is given to compounds of the formula
(III) in which R.sup.3 is an alkyl radical which is branched in the
.alpha. position and has from 4 to 40, in particular from 7 to 40,
carbon atoms and may be substituted by halogen atoms or organic
radicals having from 1 to 10 carbon atoms, in particular compounds
in which R.sup.3 is a bicyclic or polycyclic alkyl radical having
from 7 to 30 carbon atoms and optionally bearing one or more
C.sub.1-C.sub.4-alkyl radicals as substituents and in which M.sup.1
is Ti, Zr or Hf, in particular Zr or Hf, and in which X is halogen,
in particular chlorine, x is 2, LB is a cyclic or acyclic ether or
diether and y is 1 or 2.
[0088] In the process of the present invention, it is possible for
not only the desired meso compounds of the formula (I) but also the
corresponding rac compounds to be formed, where the terms meso and
rac refer to the spatial arrangement of the two cyclopentadienyl
ring systems relative to one another. For example, in cases in
which the two cyclopentadienyl radicals on the bridge are not
identical, there is no meso form having C.sub.s symmetry or rac
form having C.sub.2 symmetry, but instead there are only
diastereomeric compounds having C.sub.1 symmetry. These various
diastereomeric metallocene compounds which differ from one another
in the spatial arrangement of the different substituents behave,
when used as catalyst components in the polymerization of
propylene, like the C.sub.s-symmetric meso isomer (atactic
polypropylene) or like the C.sub.2-symmetric rac isomer (isotactic
polypropylene) simply on the basis of the spatial arrangement of
the two cyclopentadienyl ligands relative to one another and can
thus be referred to as either a pseudo-rac form or a pseudo-meso
form. ##STR10##
[0089] In the following, meso and pseudo-meso form and rac and
pseudo-rac form are distinguished simply as rac and meso forms.
[0090] Furthermore, the meso selectivity=(proportion of
meso-proportion of rac)/(proportion of rac+proportion of meso) in
the process of the present invention is greater than zero,
preferably greater than 0.5.
[0091] The salts of the formulae M.sup.2X or M.sup.2X.sub.2, for
example lithium chloride or magnesium chloride, which are obtained
as further reaction product in the process of the present invention
for preparing meso ansa-metallocenes of the formula (I) can be
separated off from the metallocene by known methods. For example, a
salt such as lithium chloride can be precipitated by means of a
suitable solvent in which the metallocene is, however, soluble, so
that the solid lithium chloride is separated off from the dissolved
metallocene by means of a filtration step. The metallocene can also
be separated off from the salt by extraction with such a solvent.
If filtration steps are employed, use can also be made of filter
aids such as kieselguhr. Organic solvents which are suitable for
such a filtration or extraction step are, in particular, organic
aprotic, oxygen-free solvents such as toluene, ethylbenzene,
xylenes and methylene chloride. If appropriate, the solvent
constituents in which the salt is at least partially soluble are
largely removed before the above-described removal of the salt. For
example, lithium chloride is appreciably soluble in
tetrahydrofuran. For this reason, an alternative is to remove the
salts of the formulae M.sup.2X and M.sup.2X.sub.2 with the aid of a
solvent or solvent mixture in which they are readily soluble while
the metallocene complex is sparingly soluble therein.
[0092] The ansa-metallocene complexes of the formula (I) prepared
by the process of the present invention are used, together with
suitable cocatalysts and, if appropriate, suitable support
materials, as constituents of a catalyst system for the
polymerization of olefins.
[0093] The present invention further provides ansa-metallocene
complexes of the formula (I) as are obtainable by the process of
the present invention and also the use of an ansa-metallocene
complex of the formula (I) prepared by a process as claimed in
claim 1 as constituent of a catalyst system for the polymerization
of olefins.
[0094] Preference is given to ansa-metallocene complexes of the
formula (I) as described above in which R.sup.3 is a bicyclic or
polycyclic alkyl radical which has from 7 to 30 carbon atoms and
may bear one or more C.sub.1-C.sub.4-alkyl radicals as
substituents, M.sup.1 is Ti, Zr or Hf, in particular Zr or Hf, X is
halogen, in particular chlorine, and x is 2.
[0095] Preference is given to metallocene mixtures which are
obtainable directly by the process of the present invention and
comprise more than 50 mol % of metallocenes of the formula (I) and
less than 50 mol % of metallocenes of the formula (Ia), based on
the total amount of metallocene compounds. Particular preference is
given to mixtures which comprise more than 75 mol % of metallocenes
of the formula (I) and less than 25 mol % of metallocenes of the
formula (Ia).
[0096] The invention is illustrated by the following nonrestrictive
examples:
EXAMPLES
General Procedures
[0097] Synthesis and handling of the organometallic compounds was
carried out in the absence of air and moisture under argon (glove
box and Schlenk technique). All solvents used were purged with
argon and dried over molecular sieves before use. NMR spectra of
organic and organometallic compounds were recorded at room
temperature on a Varian Unity-300 NMR spectrometer. The chemical
shifts are reported relative to SiMe.sub.4. [0098] 1. Synthesis of
meso-dimethylsilanediylbis(2-methylindenyl)zirconium dichloride via
intermediate isolation of
meso-dimethylsilanediylbis(2-methylindenyl)zirconium monochloride
1-adamantoxide 1a Synthesis of ZrCl.sub.4(THF).sub.2
[0099] Under protective gas, 15.2 g of zirconium tetrachloride were
suspended in 80 g of dry toluene. The suspension was cooled in an
ice bath and 12 g of tetrahydrofuran (THF) were added slowly. The
colorless suspension was subsequently stirred at room temperature
for a further one hour.
1b Synthesis of lithium 1-adamantoxide
[0100] A solution of 9.6 g of 1-adamantanol in 80 g of toluene and
12 g of THF was cooled in an ice bath and 21.2 g of a solution of
n-butyllithium (20% by weight in toluene) were added dropwise over
a period of half an hour. The reaction mixture was subsequently
stirred at room temperature for a further hour.
1c Synthesis of (THF).sub.2Cl.sub.3Zr(1-adamantoxide)
[0101] The solution of lithium 1-adamantoxide prepared in example
1b was added dropwise at room, temperature to the suspension of the
zirconium tetrachloride-THF complex prepared in example 1a over a
period of 20 minutes. The reaction mixture was stirred at room
temperature for a further 2 hours.
1d Synthesis of
Li.sub.2[dimethylsilanediylbis(2-methylindenyl)]
[0102] 42 g of a solution of n-butyllithium (20% by weight in
toluene) were added at 0-4.degree. C. to a solution of 20 g of
dimethylbis(2-methylindenyl)silane (63.30 mmol) in 132 g of toluene
and 12 g of THF over a period of 30 minutes. A yellowish beige
suspension was formed and this was stirred at room temperature for
a further 1.5 hours.
1e Synthesis and isolation of
meso-dimethylsilanediylbis(2-methylindenyl)zirconium monochloride 1
-adamantoxide (1e)
[0103] The suspension of (THF).sub.2Cl.sub.3Zr(1-adamantoxide)
prepared in example 1c was added at room temperature to the
suspension of Li.sub.2[dimethylsilanediylbis(2-methylindenyl)]
prepared in example 1d, resulting in immediate formation of a
yellow suspension. The suspension was stirred at room temperature
for a further 2.5 hours and subsequently filtered through a G4
frif. The filtercake was extracted three times with 200 g each time
of toluene. The combined filtrates were concentrated under reduced
pressure to 12% of the initial mass and allowed to stand at
-20.degree. C. for 16 hours. The yellow precipitate formed was
filtered off, washed with 15 ml of toluene and dried under reduced
pressure. This gave 6.16 g of (1e) as a yellow powder. The orange
filtercake which remained after the toluene extraction was
extracted with 200 g of dichloromethane. Removal of the solvent
under reduced pressure once again gave a yellow powder which was
washed with 30 g of heptane and subsequently dried in an oil pump
vacuum. A further 11.36 g of complex (1e) were obtained. Overall,
the complex (1e) was-obtained in a yield of 46.7% (17.52 g) in the
form of a yellow powder.
[0104] .sup.1H-NMR (CD.sub.2Cl.sub.2): 7.72 (dd, J=8.7 Hz and 1.0
Hz, 2H, aromatic), 7.22-7.19 (m, 2H, aromatic), 7.00-6.96 (m, 2H,
aromatic), 6.65-6.61 (m, 2H, aromatic), 6.25 (s, 1H, Cp), 2.52 (s,
6H, 2.times.CH.sub.3-Cp), 2.15-2.12 (m, 3H, adamantyl), 1.80-1.79
(m, 6H, adamantyl), 1.50-1.48 (m, 6H, adamantyl), 1.37 (s, 3H,
CH.sub.3Si), 1.20 (s, 3H, CH.sub.3Si).
[0105] 1 Synthesis of
meso-dimethylsilanediylbis(2-methylindenyl)zirconium dichloride (1)
2 g of acetyl chloride were added to a suspension of 10 g of the
complex (1e) prepared in example 1e in 100 ml of n-heptane. The
reaction mixture was stirred at 40.degree. C. for 5 hours. The
orange suspension was filtered through a G3 frit, the filtercake
was washed with 30 g of n-heptane and 20 g of toluene and dried
under reduced pressure. This gave 5.12 g of the compound (1) as an
orange powder (64% yield based on (1e)).
[0106] .sup.1H-NMR (CD.sub.2Cl.sub.2: 7.67 (dd, J=8.8 Hz and 0.9Hz,
2H, aromatic), 7.38-7.36 (m, 2H, aromatic), 7.11-7.07 (m, 2H,
aromatic), 6.77-6.73 (m, 2H, aromatic), 6.65 (s, 1H, Cp), 2.44 (s,
6H, 2.times.CH.sub.3-Cp), 1.43 (s, 3H, CH.sub.3Si), 1.23 (s, 3H,
CH.sub.3Si). [0107] 2. Single-vessel synthesis of meso-enriched
dimethylsilanediylbis(2-methylindenyl)zirconium dichloride (1)
without intermediate isolation of
dimethylsilanediylbis(2-methylindenyl)zirconium monochloro
1-adamantoxide
[0108] A suspension of (THF).sub.2Cl.sub.3Zr(1-adamantoxide) which
had been prepared in the same amount and in the same way as in
example 1c was added to a suspension of
Li.sub.2[dimethylsilanediylbis(2-methylindenyl)] which had been
prepared as in example 1d and the mixture was stirred at room
temperature for 2.5 hours. The yellow suspension was filtered
through a G4 glass frit filter and the filtercake was extracted
three times with 200 g each time of toluene. The filtrate was
evaporated to 50% of its original weight. 4.98 g of acetyl chloride
were added to the solution and the reaction mixture was stirred at
40.degree. C. for 3 hours. The reaction solution was concentrated
to 10% of its initial mass. The precipitate formed was filtered off
with the aid of a G3 glass frit filter, washed with 10 g of toluene
and dried under reduced pressure. This gave 4 g of the compound (1)
in the form of an orange powder (14% yield), with the rac/meso
ratio as determined by .sup.1H-NMR being 1:4. [0109] 3.
Single-vessel synthesis of meso-enriched
dimethylsilanediylbis(2-methylindenyl)zirconium dichloride (1)
without intermediate isolation of meso-enriched
dimethylsilanediylbis(2-methylindenyl)zirconium monochloride
endo-(-)-fenchoxide
[0110] The experiment was carried out in a manner analogous to
example 2. ZrCl.sub.4(THF).sub.2 was prepared in the same amount as
in example 1a and combined with a solution of lithium
endo-(-)-fenchoxide which had been prepared from 9.76 g of
endo-(-)-fenchol and 21.2 g of a solution of n-butyllithium (20% by
weight in toluene) by a method analogous to example 1b, giving a
suspension of (THF).sub.2Cl.sub.3Zr(fenchoxide). This suspension
was added to a suspension of
Li.sub.2[dimethylsilanediylbis(2-methylindenyl)] which had been
prepared as described in example 1d from 20 g of
dimethylbis(2-methylindenyl)silane (63.30 mmol). This resulted in
immediate formation of a yellow suspension which was stirred at
room temperature for 1.5 hours. The yellow suspension was filtered
through a G4 glass frit filter and the filtercake was extracted 3
times with 200 g each time of toluene. The filtrate was evaporated
to 12% of its initial mass. Some yellow crystals were able to be
isolated, and these were examined by NMR spectroscopy and found to
be dimethylsilanediylbis(2-methylindenyl)zi rconium monochloride
endo-(-)-fenchoxide.
[0111] .sup.1H-NMR (CD.sub.2Cl.sub.2: 7.66-7.63 (m,2H, aromatic),
7.27-7.15 (2dd, 2H, aromatic), 7.05-6.98 (m, 2H, aromatic),
6.69-6.65 (m, 2H, aromatic), 6.58 and 6.36 (2s, 2H, 2.times.Cp),
3.91 (s, 1H, fenchyl), 2.53 and 2.49 (2s, 6H, 2.times.CH.sub.3-Cp),
1.36, 1.20 and 1.18 (3s, 9H, CH.sub.3-fenchyl), 1.03 (s, 3H,
CH.sub.3Si), 0.92 (s, 3H, CH.sub.3Si), 1.69-1.30, 1.10-1.04, 0.98
and 0.85-0.77 (m, H, fenchyl).
[0112] 4.97 g of acetyl chloride were added to the partly
evaporated solution and the reaction mixture was stirred at
40.degree. C. for one hour. The precipitate was filtered off with
the aid of a G3 glass frit filter, washed with 40 g of n-heptane
and dried under reduced pressure. This gave 4.51 g of the compound
(1) in the form of an orange powder (14% yield), with the rac/meso
ratio as determined by .sup.1H-NMR being 1:6.
* * * * *